CN106999912A - Catalyst carrier, its manufacture method and application thereof - Google Patents
Catalyst carrier, its manufacture method and application thereof Download PDFInfo
- Publication number
- CN106999912A CN106999912A CN201580066485.7A CN201580066485A CN106999912A CN 106999912 A CN106999912 A CN 106999912A CN 201580066485 A CN201580066485 A CN 201580066485A CN 106999912 A CN106999912 A CN 106999912A
- Authority
- CN
- China
- Prior art keywords
- carbon
- catalyst carrier
- catalyst
- particle
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 221
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 149
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 136
- 239000002245 particle Substances 0.000 claims abstract description 131
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 106
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000446 fuel Substances 0.000 claims abstract description 51
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- -1 titanium compound carbon compound Chemical class 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 52
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 21
- 239000006229 carbon black Substances 0.000 claims description 18
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 229910017052 cobalt Inorganic materials 0.000 claims description 17
- 239000010941 cobalt Substances 0.000 claims description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 150000002739 metals Chemical class 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 239000011164 primary particle Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000002923 metal particle Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- OKJADYKTJJGKDX-UHFFFAOYSA-N Butyl pentanoate Chemical compound CCCCOC(=O)CCCC OKJADYKTJJGKDX-UHFFFAOYSA-N 0.000 claims 1
- WDEBGAIWHWRDCF-UHFFFAOYSA-N [C].[N].[Ti] Chemical compound [C].[N].[Ti] WDEBGAIWHWRDCF-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 230000007423 decrease Effects 0.000 abstract description 12
- 239000010410 layer Substances 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 16
- 230000008859 change Effects 0.000 description 14
- 230000009102 absorption Effects 0.000 description 13
- 230000005540 biological transmission Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 229910000531 Co alloy Inorganic materials 0.000 description 10
- 229910001260 Pt alloy Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005087 graphitization Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011852 carbon nanoparticle Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CYKMNKXPYXUVPR-UHFFFAOYSA-N [C].[Ti] Chemical compound [C].[Ti] CYKMNKXPYXUVPR-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PIZYHTQSHRQOBI-UHFFFAOYSA-N [C].O=[N] Chemical compound [C].O=[N] PIZYHTQSHRQOBI-UHFFFAOYSA-N 0.000 description 1
- RGSBWMSEZLEFRP-UHFFFAOYSA-N [N]=O.[Ti].[C] Chemical class [N]=O.[Ti].[C] RGSBWMSEZLEFRP-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
- B01J35/45—Nanoparticles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
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- H01M4/90—Selection of catalytic material
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Abstract
The problem of the present invention is that offer hydraulic performance decline under low humidified condition is also small and shows the manufacture method of the catalyst carrier of high-durability, electrode catalyst, the electrode comprising the catalyst, the membrane-electrode assembly with the electrode, the fuel cell for possessing the membrane-electrode assembly and catalyst carrier.The present invention is a kind of catalyst carrier, it is the catalyst carrier of the carbon material comprising the chain structure being connected with carbon particle, the catalyst carrier contains the titanium compound carbon compound particle of the particle of the internal package titanium compound of carbon, elemental mole ratios in catalyst carrier, when titanium is set into 1, carbon is more than 0 and is that less than 50, nitrogen is more than 0 and is that less than 2, oxygen is more than 0 and be less than 3.
Description
Technical field
The present invention relates to catalyst carrier, electrode catalyst, the electrode comprising the electrode catalyst, the film with the electrode
The manufacture method of assembly of electrode, the fuel cell for possessing the membrane-electrode assembly and catalyst carrier.
Background technology
Polymer electrolyte fuel cell, which is mainly used, supports the catalyst metals containing platinum in carbon-supported body
Electrode catalyst.But, the carbon carrier used as conventional catalyst carrier is out of service contour in the starting of fuel cell
It is oxidized easily under current potential operation, therefore cohesion, disengaging etc. occur for the catalyst metals supported, this turns into electrode catalyst
The main cause of performance degradation.
In addition, the load of the accessory in order to reduce fuel cell system, it is desirable to which the gas of supply is in the state of low humidification
Fuel cell operation.But, if fuel cell is run in the state of the low humidification, due to (dry up) phenomenon that dries up
The proton conductive of the ionomer in dielectric film and catalyst layer is set to be deteriorated, therefore the power output of fuel cell declines.
In patent document 1, in order that the durability of the carbon carrier under high potential operation is improved, carbon load is improved by being heat-treated
The crystallization degree of body, makes carbon carrier become to be difficult to be oxidized under fuel cell operation.But, the only heat treatment by carbon carrier is difficult
To expect the high oxidation resistance of carbon carrier during high potential operation, particularly it is difficult to prevent the combustion during operation under low humidification state
Expect the hydraulic performance decline of battery.In addition, if using the high carbon carrier of degree of graphitization, although then corrosion resistance is improved, carbon carrier
Specific surface area declines, therefore power generation performance declines.
Recorded in patent document 2 for a kind of electrode catalyst, the electrode catalyst in order to maintain catalysis
The high activity of agent and improve durability, the carbon carrier of catalyst-loaded metal and acidic oxide have been carried out into physics mixes
Close.But, the hydrophobicity of carbon carrier is high, and the hydrophily of acidic oxide is high, therefore these are had to the catalysis of different physical property
Equably physical mixed is extremely difficult for agent carrier, and uneven physical mixed can turn into catalyst performance inequality, catalyst layer
The reason for hydraulic performance decline caused by irregular, cracking etc. is produced during coating.
In patent document 3, disclose to also maintain battery performance to a certain extent under the operation of low humidification state, it is right
Anode uses the catalyst material of the hydrophilic particles comprising zeolite, titanium dioxide etc..But, these catalyst materials do not possess
Electrical conductance, therefore the internal resistance of anticipation catalyst layer can become big.
In patent document 4, a kind of fuel cell carrier carbon for mixing moisture retention carbon material and carbon black is disclosed
Material.In the technology, can expect to a certain extent the carbon material that the carbon material of activation process is brought vapor absorb and
Release, but in the fuel cell operation under low humidification state, the ionomer in dielectric film and catalyst layer is possessed water conservation
Property aspect it is insufficient, it is impossible to expect high cell output.In addition, the carbon material is in order that carbon material possesses moisture retention and entered
The carbon material that micropore of having gone is imported, so being very easy to be oxidized under the high potential operation of fuel cell, it is possible to also produce
The problem of durability.
Citation
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2001-357857 publications
Patent document 2:Japanese Unexamined Patent Publication 2013-33701 publications
Patent document 3:Japanese Unexamined Patent Publication 2004-342505 publications
Patent document 4:Japanese Unexamined Patent Publication 2013-20793 publications
The content of the invention
It is also small and display high-durability it is an object of the invention to provide a kind of hydraulic performance decline under low humidified condition
It is supplied to carrier, electrode catalyst, the electrode comprising the catalyst, the membrane-electrode assembly with the electrode, the tool of catalyst
The fuel cell and the manufacture method of catalyst carrier of the standby membrane-electrode assembly.
The present invention includes the invention of following [1]~[24].
[1] a kind of catalyst carrier, includes the carbon material for the chain structure being connected with carbon particle, and the catalyst is carried
Body includes titanium compound carbon compound particle, and the titanium compound carbon compound particle is the particle in the internal package titanium compound of carbon
Obtained from, the mol ratio of the element in catalyst carrier, when titanium is set into 1, carbon be more than 0 and for less than 50, nitrogen be more than 0 and
For less than 2, oxygen is more than 0 and is less than 3.
[2] catalyst carrier according to preceding paragraph [1], dibutyl phthalate oil absorption is 150~450mL/
100g。
[3] catalyst carrier according to preceding paragraph [1] or [2], the content of the titanium compound particle is 10~90 matter
Measure %.
[4] catalyst carrier according to any one of preceding paragraph [1]~[3], BET specific surface area is 450~1100m2/
g。
[5] catalyst carrier according to any one of preceding paragraph [1]~[4], the particle of the titanium compound is averaged
Particle diameter is 5~300nm.
[6] catalyst carrier according to any one of preceding paragraph [1]~[5], in the titanium compound carbon compound particle
In, the carbon of the particle of internal package titanium compound is at least one kind of carbon in amorphous carbon and graphitized carbon.
[7] catalyst carrier according to any one of preceding paragraph [1]~[6], the carbon material is selected from carbon black, graphite
Change wantonly a kind in carbon black, graphite and porous carbon.
[8] catalyst carrier according to any one of preceding paragraph [1]~[6], the carbon material is to be selected from carbon black, graphite
Change the mixture for appointing two or more to mix in carbon black, graphite and porous carbon.
[9] catalyst carrier according to any one of preceding paragraph [1]~[8], the primary particle size of the carbon material for 5~
300nm。
[10] a kind of electrode catalyst, is to be supported with catalysis to the catalyst carrier described in any one of preceding paragraph [1]~[9]
Obtained from agent metallic.
[11] electrode catalyst according to preceding paragraph [10], the metals of the catalyst metal particles be selected from platinum, palladium,
At least one kind of metal in ruthenium, gold, rhodium, iridium, osmium, iron, cobalt, nickel, chromium, zinc and tantalum or by least two kinds of in these metals
The alloy that metal is constituted.
[12] electrode catalyst according to preceding paragraph [10] or [11], BET specific surface area is 200~800m2/g。
[13] a kind of electrode, has:Electrode matrix and the catalyst layer formed on the electrode matrix, the catalyst
The electrode catalyst that any one of the layer comprising preceding paragraph [10]~[12] is recorded.
[14] a kind of membrane-electrode assembly, is that negative electrode and anode are configured across dielectric film, the negative electrode and institute
It is the electrode described in preceding paragraph [13] to state at least one party of anode.
[15] a kind of fuel cell, possesses the membrane-electrode assembly described in preceding paragraph [14].
[16] a kind of manufacture method of catalyst carrier, is to manufacture the catalyst described in any one of preceding paragraph [1]~[9]
The method of carrier, including:By the carbon material and the internal package titanium compound of carbon of the chain structure being connected with carbon particle
Particle the mixing of titanium compound carbon compound particle process, the ratio between the element in the titanium compound compound particle,
When titanium is set into 1, carbon is more than 0 and is that less than 7, nitrogen is more than 0 and is that less than 2, oxygen is more than 0 and be less than 3.
[17] manufacture method of the catalyst carrier according to preceding paragraph [16], the titanizing relative to 1 mass parts is closed
Thing carbon compound particle, mixes the carbon material of 0.1~10 mass parts.
[18] manufacture method of the catalyst carrier according to preceding paragraph [16] or [17], the BET of the carbon material compares table
Area is 700~1400m2/g。
[19] manufacture method of the catalyst carrier according to any one of preceding paragraph [16]~[18], the carbon material
Dibutyl phthalate oil absorption is 350~550mL/100g.
[20] manufacture method of the catalyst carrier according to any one of preceding paragraph [16]~[19], the carbon material
Crystallite dimension is 0.6~2.0nm.
[21] manufacture method of the catalyst carrier according to preceding paragraph [16] or [17], the carbon material is that BET compares table
Area is 700~1400m2/ g carbon material X and BET specific surface area is 100~500m2/ g carbon material Y mixture.
[22] manufacture method of the catalyst carrier according to preceding paragraph [21], the primary particle size of the carbon material Y for 5~
300nm, and crystallite dimension is 2.0~5.0nm.
[23] manufacture method of the catalyst carrier according to any one of preceding paragraph [16]~[22], by the way that titanium will be selected from
At least one kind of compound in carbon nitrogen oxide, titanyl nitride and titanium oxide is mixed with polyvinylpyrrolidone, non-oxidizable
It is heat-treated under gas atmosphere with 500~1100 DEG C, obtains the titanium compound carbon compound particle.
[24] manufacture method of the catalyst carrier according to any one of preceding paragraph [16]~[23], the titanium compound
Particle BET specific surface area be 50~300m2/g。
According to the present invention, a kind of catalyst carrier is can obtain, it can obtain the runnability under low humidified condition
Decline catalyst that is also small and being able to maintain that high-output power.Even if in addition, the fuel cell obtained using the catalyst carrier
Also there is high-durability in load change and starting are out of service.
Brief description of the drawings
Fig. 1 is the carbon particle B (1) obtained in embodiment 1 transmission electron microscope picture.
Fig. 2 is the transmission electron microscope picture of the electrode catalyst (2) obtained in embodiment 1.
Embodiment
(catalyst carrier)
The catalyst carrier of the present invention, comprising:The chain structure being connected with carbon particle (will form chain sometimes below
The carbon particle of shape structure is referred to as " carbon particle A ") carbon material and titanium compound carbon compound particle (hereinafter sometimes referred to " carbon particle
B "), the titanium compound carbon compound particle be the internal package titanium compound of carbon particle (hereinafter sometimes referred to " titanizing close
Thing particle ") obtained from, the mol ratio of the element in the catalyst carrier, when titanium is set into 1, carbon be more than 0 and for 50 with
Under, nitrogen is more than 0 and is that less than 2, oxygen is more than 0 and be less than 3.
The BET specific surface area of the catalyst carrier, from the viewpoint of catalyst performance described later, preferably 450~
1100m2/ g, more preferably 700~1100m2/ g, particularly preferably 900~1100m2/g。
The dibutyl phthalate oil absorption (hereinafter also referred to " DBP oil absorptions ") of the catalyst carrier, from aftermentioned
Catalyst performance from the viewpoint of, preferably 150~450mL/100g, more preferably 200~450mL/100g.
The content of the titanium compound particle in the catalyst carrier, goes out from the viewpoint of catalyst performance described later
Hair, particularly preferably preferably 10~90 mass %, more preferably 20~80 mass %, 30~70 mass %.Wherein, it will be catalyzed
Agent carrier is integrally set to 100 mass %.
The titanium compound of the titanium compound particle is constituted, from being readily available from the viewpoint of high catalyst performance, as
Element preferably comprises carbon, nitrogen and/or oxygen.
The titanium compound particle, from the viewpoint of durability and water-retaining property is improved, average grain diameter is preferably 5~
300nm, more preferably 5~200nm, particularly preferably 5~100nm.Furthermore, the average grain diameter is by transmission electron microscope
Observation, the calculation of the particle diameter of each particle obtained from the diameter of the titanium compound particle of more than 50 to selecting at random is measured
Art average value.
Internally wrap up the titanium compound particle carbon be preferably selected from amorphism carbon and graphitized carbon at least 1
Plant carbon.I.e., it is possible to be the high carbon (graphitized carbon) of the high carbon of amorphism (amorphous carbon), degree of graphitization, can also be these
Carbon is mixed.From it is further improve durability and water-retaining property from the viewpoint of, preferably graphitized carbon.
The mol ratio of the element of the titanium compound carbon compound particle, when titanium is set into 1, be preferably:Carbon is more than 0 and is
Less than 7, nitrogen is more than 0 and is that less than 2, oxygen is more than 0 and be less than 3, more preferably:Carbon is more than 0 and is that less than 5, nitrogen is more than 0 and is
Less than 1, oxygen is more than 0 and is less than 2.
As the carbon material, appointing in carbon black, Graphon, graphite and porous carbon can be suitably used
1 kind of carbon material.The manufacture method of Graphon is described below.
As carbon material, from being readily obtained from the viewpoint of high catalyst performance, can also suitably use selected from carbon black,
Two or more any mixture for mixing in Graphon, graphite and porous carbon.Carbon material be more preferably carbon black with
The mixture of Graphon.
Carbon black is made up of carbon particulate with chain structure, and carbon particulate is made up of amorphous carbon, carbon black according to
Its manufacture method is classified as furnace black, acetylene black, thermals etc., but any catalyst carrier that can serve as is used.
The specific surface area of carbon black is fully big, if included by catalyst carrier, is readily obtained high initial voltage.
Graphon can by by commercially available carbon black heated under inertia or reducibility gas atmosphere come
Obtain.Graphon degree of graphitization compared with carbon black is big, if included by catalyst carrier, is readily obtained durability.
As carbon material, it is also preferred that the mixture of two or more carbon materials.In this regard, " manufacturer of catalyst carrier
The narration in detail of method " part.
Graphon can also have the overlapping micro-structure of graphite linings in its carbon particulate.Work as graphitized charcoal
In the case of black micro-structure overlapping with graphite linings in its carbon particulate, the number of plies of the layer structure is preferably 1
~30, more preferably 1~20.When the number of plies is in the scope, initial activity is high, be readily obtained start it is out of service under it is durable
Property.Furthermore, the number of plies is the layer structure in 50 Graphons selected at random by transmission electron microscope observation
The arithmetic mean of instantaneous value of the number of plies.Graphon has the overlapping micro-structure of graphite linings in its carbon particulate, and this also may be used
To be confirmed by degree of graphitization.
The primary particle size of the carbon material, from being readily obtained from the viewpoint of high catalyst performance, preferably 5~300nm,
More preferably 5~100nm, particularly preferably 5~50nm.Furthermore, the primary particle size is that the transmission electron for carrying out carbon material shows
When micro mirror is observed, the arithmetic that the diameter of 50 carbon particle A to selecting at random is measured obtained each carbon particle A particle diameter is put down
Average.
(manufacture method of catalyst carrier)
The manufacture method of the catalyst carrier of the present invention can obtain the catalyst carrier, be not particularly limited.As
The present invention catalyst carrier manufacture method, can enumerate for example, by with carbon particle be connected chain structure carbon materials
Material and the process (hereinafter sometimes referred to (c) process) of titanium compound carbon compound particle (carbon particle B) mixing, the titanium compound
Carbon compound particle is the member in the titanium compound carbon compound particle obtained from the particle of the internal package titanium compound of carbon
The ratio between element, when titanium is set into 1, carbon is more than 0 and is that less than 7, nitrogen is more than 0 and is that less than 2, oxygen is more than 0 and be less than 3.
As the present invention catalyst manufacture method, can before (c) process, for example with:(a) it will be selected from
At least one kind of compound (hereinafter sometimes referred to " starting compound ") in titanium carbon nitrogen oxides, titanyl nitride and titanium oxide with
Polyvinylpyrrolidone is mixed, the process for obtaining mixture;(b) by the mixture under non-oxidizing gas atmosphere with 500
~1100 DEG C are heat-treated, the process for thus obtaining titanium compound carbon compound particle.Furthermore, by (a) processes and (b) process
Obtained titanium compound carbon compound particle, is the titanium for the particle that the internal package of carbon contains the titanium compound of carbon, nitrogen and oxygen
Compound carbon compound particle.In this case, the particle of the titanium compound by the way that the internal package of the carbon to be contained to carbon, nitrogen and oxygen
Titanium compound carbon compound particle be used as carbon particle B, the carbon material of the chain structure being connected with carbon particle is mixed
Close, catalyst carrier can be obtained.
Generally, it is the hydrophilic particles of the carbon material and titanium compound etc of hydrophobic conductive carbon particle etc are uniform
Mixing is difficult, but the titanium compound particle used in the present invention is wrapped in inside carbon, therefore both easily uniform mixing.
Therefore, the incorporation time when carbon material is mixed with carbon particle B was generally enough at 10 minutes~10 hours or so
's.In addition, both are uniformly mixed, thus can expect the maintenance of humidity in electrode described later and the raising of electron conduction,
The deterioration of load change and the starting catalyst out of service brought is small, the decline of catalyst performance under low humidified condition
Also it is small.
In the mixing and (c) process of the particle and polyvinylpyrrolidone of starting compound in (a) process
Carbon material and carbon particle B mixing, can enumerate and the method that method is carried out is kneaded using solid phase.Method is kneaded as solid phase, preferably
The method of even mixing, can enumerate for example using roller rotate grinding machine, ball mill, path ball mill (ball mill), medium stirring mill machine,
Airslide disintegrating mill, mortar, automatic mixing mortar, the method for groove solution machine or jet mill.
As for used in (b) process, the gas of the non-oxidizing gas atmosphere, indifferent gas can be enumerated
Body, hydrogen, in less expensive and on this point of being readily available preferably nitrogen, argon gas, helium, more preferably nitrogen and argon gas.These
Gas can use independent a kind, can also be mixed with two or more.
As the magnitude relation of carbon particle B and carbon material used in (c) process, in obtained catalyst carrier,
Use as the mol ratio of each element during so that titanium being set to 1 turns into above range, is not particularly limited, preferably with respect to
The carbon particle B of 1 mass parts, mixes the carbon material of 0.1~10 mass parts, more preferably mixes 0.1~5 mass parts, especially excellent
Choosing 0.4~3 mass parts of mixing.If the magnitude relation of carbon particle B and carbon material is in the scope, more it can reduce and humidify
Under the conditions of low humidified condition of initial voltage when comparing under initial voltage decline.
The BET specific surface area of the titanium compound particle, Composite from titanium compound particle and the carbon material, is carried on a shoulder pole
From the viewpoint of the dispersiveness and micronized of the catalyst metals of load, preferably 50~300m2/ g, more preferably 100~300m2/
g。
The DBP oil absorptions of the carbon material, from the viewpoint of electron conduction and mixed characteristic, preferably 350~
550mL/100g, more preferably 400~550mL/100g, particularly preferably 450~550mL/100g.
The BET specific surface area of the carbon material, from catalyst metals support dispersiveness and micronized from the viewpoint of, it is excellent
Elect 700~1400m as2/ g, more preferably 800~1400m2/ g, particularly preferably 1000~1400m2/g。
The degree of graphitization of carbon material is with the size Lc in the c-axis direction of crystallite (be also sometimes referred to as below " crystallite dimension ") table
Show.
The carbon material in the present invention, crystallite dimension is preferably 0.6~2.0nm, more preferably 0.8~2.0nm, especially
Preferably 0.8~1.6nm.If crystallite dimension more than 0.6nm, then the degree of graphitization of carbon nano-particles is high, is readily obtained fuel
Durability under the load change of battery and starting are out of service.If crystallite dimension below 2nm, then big ratio table is readily obtained
Area, is readily obtained high catalyst performance.
As the carbon material, from the viewpoint of durability and initial performance is had concurrently, two kinds can also be suitably used
The mixture of carbon material above.The mixture mixed when 2 kinds of carbon materials that carbon material is carbon material X and carbon material Y
In the case of, carbon material X BET specific surface area is preferably 700~1400m2/ g, more preferably 800~1400m2/ g, particularly preferably
For 900~1400m2/g.Carbon material Y BET specific surface area is preferably 100~500m2/ g, more preferably 100~400m2/ g, it is special
You Xuanwei not 100~350m2/g.When the BET specific surface area of 2 kinds of carbon materials is respectively at the scope, initial activity is high, easy
To durability of the starting under out of service.
In the case that carbon material is the mixture of carbon material X and carbon material Y 2 kinds of carbon materials, 10~90 matter are preferably used
The carbon material X of part is measured, and using the carbon material Y of 10~90 mass parts, more preferably using the carbon material X of 30~70 mass parts, and
Use the carbon material Y of 30~70 mass parts.Wherein, the total of carbon material X and carbon material Y is set to 100 mass parts.
The primary particle size of carbon material Y with above-mentioned BET specific surface area, from the viewpoint for being readily obtained high catalyst performance
Set out, preferably 5~300nm, more preferably 5~100nm, particularly preferably 5~50nm.Furthermore, the primary particle size is to carry out
During carbon material Y transmission electron microscope observation, the diameter of 50 carbon particle A to selecting at random is measured obtain each
The arithmetic mean of instantaneous value of the particle diameter of carbon particle.
The crystallite dimension of carbon material Y with above-mentioned BET specific surface area is preferably 2.0~5.0nm, and more preferably 2.0
~4.5nm, particularly preferably 2.5~4.5nm.Crystallite dimension be in the scope when, be readily obtained start it is out of service under it is resistance to
Long property.
Carbon material Y with physics value as described above, can be suitably using among commercially available carbon material as raw material
The carbon material being made up of carbon particulate with chain structure, carbon particulate is made up of amorphous carbon, can be commercially available by this
Carbon material under inertia or reducibility gas atmosphere with 2200~3000 DEG C carry out such as 4 hours heat and obtain.Make
It is that inertia or reducibility gas atmosphere can use foregoing atmosphere.
As the carbon material Y for both important documents for having above-mentioned primary particle size and crystallite dimension concurrently, it can enumerate for example
Graphon.Such Graphon can be by the way that carbon black be heated under inertia or reducibility gas atmosphere
To obtain, degree of graphitization is big compared with carbon black for it, if included by catalyst carrier, is readily obtained durability.
(electrode catalyst)
The electrode catalyst of the present invention, is obtained from making the catalyst-loaded metallic of the catalyst carrier.
The metal of the catalyst metal particles, from being readily obtained from the viewpoint of high catalyst performance, is preferably selected from
At least one kind of metal in platinum, palladium, ruthenium, gold, rhodium, iridium, osmium, iron, cobalt, nickel, chromium, zinc and tantalum or by 2 kinds among the metal with
On the alloy that constitutes of metal, more preferably platinum or platinum alloy.
As the alloy be platinum alloy when platinum beyond alloying component, be preferably selected from palladium, ruthenium, gold, rhodium, iridium, osmium,
At least one kind of metal in iron, cobalt, nickel, chromium, zinc and tantalum, more than a kind of metal being preferably selected from palladium, ruthenium, iron and cobalt, more
More than a kind of metal being preferably selected from palladium and cobalt, particularly preferably cobalt.These are used by being used as catalyst metal component
Composition, is readily obtained good catalyst activity.
The average grain diameter of the catalyst metal particles is preferably 2~10nm, more preferably 3~7nm.If the degree
Average grain diameter, then catalyst activity become good, fuel cell environment stability inferior also by it is easy to ensure that, durability is improved, therefore
It is preferred that.The assay method of the average grain diameter of catalyst metal particles can be using the average grain diameter with foregoing titanium compound particle
Same method is carried out.
In addition, the ratio of the catalyst metals contained by electrode catalyst entirety is preferably 20~70 mass %, it is more excellent
Elect 30~50 mass % as.If the scope then easily suppresses cohesion and the coarsening of catalyst metals, easily make catalyst performance
It can improve, therefore preferably.
The BET specific surface area of the electrode catalyst, from being readily obtained from the viewpoint of high catalyst performance, be preferably
200~800m2/ g, more preferably 200~700m2/ g, particularly preferably 200~600m2/g。
(electrode)
The electrode catalyst can be processed into by ink using method and usual method described later for implementing to exemplify etc..
By the way that obtained ink is coated with to electrode matrix, the catalyst for including the electrode catalyst is formed on electrode matrix surface
Layer, can obtain the electrode of the present invention.That is, electrode of the invention has:Electrode matrix and be formed on include the electricity
The catalyst layer of electrode catalyst.Furthermore, in the case that the electrode of the present invention is used as into the electrode of fuel cell, preferred electrode base
Body has gas diffusion layers on its surface.In addition, the electrode of the present invention may be used as negative electrode, anode is also used as, can be with
As negative electrode and anode.
The electrode of the present invention may be used as the negative electrode of fuel cell.In this case, can obtain in low humidified condition
The decline of lower catalyst activity is small, in load change and the high fuel cell of starting middle durability out of service.
The electrode is also used as the anode using hydrogen as the fuel cell of fuel.In this case, low humidification can be formed
The small electrode of decline of hydroxide activity under environment.
In addition, the electrode may be used as the anode using alcohol as the fuel cell of fuel.In this case, table of the alcohol in electrode
Face is easily wetted, and can obtain high alcohol oxidation activity.
(membrane-electrode assembly)
The membrane-electrode assembly of the present invention is negative electrode and anode to be configured across dielectric film, the negative electrode and the anode
At least one is constituted with the electrode of the invention.
(fuel cell)
The fuel cell of the present invention possesses the membrane-electrode assembly.Accordingly, it is capable to access high-output power and durability
High fuel cell.
Embodiment
Embodiments of the invention described below, further illustrate the present invention.Furthermore, these are one of the present invention, this
Invention is at all not limited to this.In addition, the quantitative elementary analysis, DBP oil absorptions in embodiment and comparative example are determined, BET compares table
Area estimation, transmission electron microscope observation and crystallite dimension are determined, and are carried out using following method.
1. quantitative elementary analysis
Carbon:About 0.1g samples are measured, making institute EMIA-110 using hole is determined.
Nitrogen and oxygen:About 0.1g samples are measured, is put into after nickel cup (Ni-Cup) sealing, is surveyed using ON analytical equipments
It is fixed.
Metallic element:About 40mg samples are weighed into beaker, chloroazotic acid is added, sulfuric acid is subsequently added into and carries out heat resolve.Will
The heat resolve thing is with after ultra-pure water constant volume, and appropriate dilution is right using ICP apparatus for analyzing luminosity (SII company system VISTA-PRO)
Metallic element is quantified.
2.DBP oil absorptions are determined
DBP oil absorptions use absorption apparatus (ア ブ ソ ー プ ト メ ー タ ー, Branbender company system), by peak torque
70% when DBP additions as every 100g samples DBP oil absorptions conversion be determined.
3.BET specific area measurings
BET specific surface area is determined using マ ッ ク ソ ー プ (Macsorb, Co., Ltd.'s マ ウ Application テ ッ Network systems), uses nitrogen
Gas, calculates the specific surface area of sample.Pretreatment time, the pretreatment temperature of measure are respectively set as 30 minutes, 200 DEG C.
4. transmission electron microscope is observed
Transmission electron microscope (TEM) observation is carried out using Hitachi H9500 (accelerating potential 300kV).See
Examining sample, ultrasonic wave disperses to obtain dispersion liquid in ethanol by making sample powder, and by the dispersion liquid in tem observation grid
(grid) drip down making on.
5. crystallite dimension
Use Rigaku Denki Co., Ltd X-ray diffraction device Rotor Flex (ロ ー タ Off レ ッ Network ス), carry out
The powder x-ray diffraction of sample.As X-ray diffraction measure condition, the measure model using the 50kW of Cu-K α lines at 10~90 °
Enclose and analyzed.Now, will be at 20 °<2θ<The peak of 30 ° of appearance is calculated by Scherrer formula, tries to achieve crystallite dimension.
[embodiment 1]
(carbon particle B (1) making)
1.2g carbon (キ ャ ボ ッ ト (Cabot) company system, Vulcan 72) is fully crushed and the titanium dioxide commercially available with 5g
Particle is mixed.By the mixed-powder in tube furnace, heated with 1600 DEG C, 1 hour in nitrogen atmosphere, thus
Titanium carbon nitride is arrived.By obtained titanium carbon nitride in the state of the nitrogen of oxygen of the circulation containing 1 capacity %, with 800
DEG C carry out 1 hour be heat-treated, resulting in titanium compound (1).Obtained titanium compound particle is broken using ball mill
It is broken.
Titanium compound described in 5g (1) and 5g polyvinylpyrrolidones (Nippon Catalyst K. K.'s system) are used into ball mill
Uniform mixing, has obtained solid mixed-powder.The powder is put into tube furnace, in the hydrogen and nitrogen of the hydrogen containing 4 volume %
700 DEG C are heated under the mixed-gas atmosphere of gas, carries out being heat-treated for 1 hour at 700 DEG C, the internal package titanium of carbon particle has been obtained
The titanium compound carbon compound particle (be also denoted as below " carbon particle B (1) ") of compound particles.In the carbon particle B (1)
The mol ratio of element, when titanium is set into 1, carbon is that 4.36, nitrogen is that 0.04, oxygen is 1.96.By the transmission of the carbon particle B (1)
Type electron microscopic mirror image is shown in Fig. 1.In figure, (1) represents the particle of titanium compound (1), and (2) represent to constitute carbon particle B's (1)
Carbon.
(making of catalyst carrier)
By commercially available carbon material (BET specific surface area 1350m2/ g, DBP oil absorptions 490mL/100g, crystallite dimension 1.5nm,
Carbon particle (it is also denoted as below " carbon particle A (1) ") be connected the carbon material with chain structure) (hereinafter, also referred to as " carbon material
(1) ") and carbon particle B (1), mixed using ball mill, obtained catalyst carrier (1).Furthermore, relative to catalyst carrier
(1) gross mass, 50 mass % are set to by the ratio of the carbon particle B (1).In addition, element in catalyst carrier (1) rubs
You compare, and when titanium is set into 1, carbon is that 18.60, nitrogen is that 0.04, oxygen is 1.96.
(supporting for catalyst component)
To 1L pure water addition 0.20g catalyst carriers (1), it is set to vibrate more than 30 minutes using sonic washing machine.Will
Obtained suspension is maintained 80 DEG C of liquid temperature, stirs more than 30 minutes.Here, 0.517g chlorination platinic acid hexahydrates will be included
The aqueous solution 40mL of (being 0.195g as platinum) and 0.083g cobalt acetates (II) tetrahydrate (being 0.020g as cobalt) is small with 1
When drip.Now, by the 1.0mol/L sodium hydrate aqueous solutions that suitably drip, the pH value of suspension is maintained at about 7.0.So
Afterwards, stirred 3 hours in the state of the temperature of suspension is maintained into 80 DEG C.Then, by the sodium borohydride containing 0.583g
Aqueous solution 60ml was dripped to above-mentioned suspension with 30 minutes.Then, stirred in the state of the liquid temperature of suspension is maintained into 80 DEG C
Mix 1 hour.After reaction terminates, above-mentioned suspension is cooled to room temperature, black powder is filtered off by filtering, and be dried.
(heat treatment)
The black powder is put into quartzy tube furnace, in the hydrogen and the gaseous mixture of nitrogen of the hydrogen containing 4 volume %
Under body atmosphere, 700 DEG C are heated to 10 DEG C/min of warming temperature, the heat treatment of 30 minutes is carried out at 700 DEG C, thus makes platinum
With cobalt alloyization formation Pt-Co alloys, the electrode catalyst for having supported the alloy as catalyst metals has been obtained (below
It is designated as " electrode catalyst (1) ").The transmission electron microscope picture of electrode catalyst (1) is shown in Fig. 2.In Fig. 2, (3) are represented
Carbon particle B (1), (4) represent that carbon particle A (1), (5) represent catalyst metals (Pt-Co alloys).It is can confirm that by Fig. 2 in electrode
In catalyst (1), two sides on carbon particle B and on carbon particle A are uniformly dispersed being supported with catalyst metals.
(making and its evaluation of fuel cell)
(1) modulation of negative electrode ink
By electrode catalyst (1) 35mg, contain proton conductive material (Na Off ィ オ Application (NAFION) (registration mark))
The 15.8mg aqueous solution (the 5%NAFION aqueous solution and the pure medicine system of light)) 0.315g, pure water 2.0mL, 2- propyl alcohol 2.0mL be weighed to
In bottle (vial), 30 minutes ultrasonic waves of progress wash irradiation in frozen water, thus modulate negative electrode black (1).
(2) making of negative electrode
Gas diffusion layers (carbon paper (eastern beautiful TGP-H-060 processed)) are impregnated in acetone 30 seconds and carried out after degreasing, do it
It is dry, then impregnated 30 seconds in 10% polytetrafluoroethylene (PTFE) (PTFE) aqueous solution.It will impregnate after thing drying at room temperature, add at 350 DEG C
Heat 1 hour, resulting in carbon paper inner dispersion PTFE and with hydrophobicity gas diffusion layers (be also denoted as below "
GDL”).Then, on the surface for the GDL for being formed as 5cm × 5cm sizes, auto spraying apparatus for coating (サ Application エ イ are passed through
テ ッ Network company system), in 80 DEG C of coated cathodes with black (1), make the electrode that there is cathode catalyst layer (1) on GDL surfaces
The total amount of electrode catalyst (1) is unit area in (be also denoted as below " negative electrode (1) "), the cathode catalyst layer (1)
0.20mg/cm2。
(3) modulation of anode ink
Added to pure water 50ml C catalyst (the Tanaka's noble metal industry processed TEC10E70TPM) 0.6g that is supported with platinum and
The aqueous solution (the 5%NAFION aqueous solution and the pure medicine system of light) containing proton conductive material 0.25g) 5g, uses ultrasonic dispersing machine
Mixing 1 hour, has thus modulated anode black (1).
(4) making of anode
Obtain being formed as the GDL of 5cm × 5cm sizes in the same manner as making with foregoing negative electrode, be coated with using auto spraying
Device (サ Application エ イ テ ッ Network company system), above-mentioned anode is coated with 80 DEG C with black (1) to the GDL surfaces, made in GDL tables
Face, which has in the electrode (be also denoted as below " anode (1) ") of anode catalyst layer (1), the anode catalyst layer (1), to be supported with
The total amount of the C catalyst of platinum is unit area 1.00mg/cm2。
(5) making of membrane-electrode assembly
NAFION films (NR-212, DuPont system), the negative electrode as negative electrode as dielectric film are prepared respectively
(1), as the anode (1) of anode.Make as follows and be configured with the dielectric film between negative electrode (1) and anode (1)
Fuel battery membrane electrode assembly (it is also denoted as below " MEA ").The dielectric film is clamped with negative electrode (1) and anode (1),
In the way of cathode catalyst layer (1) and anode catalyst layer (1) are in close contact with the dielectric film, using hot press in temperature
It is attached that 140 DEG C of degree, pressure 3MPa carried out hot pressing with 7 minutes to them, has made MEA (1).
(6) making of element cell
MEA (1) is added with 2 seals (pad), 2 dividing plate, 2 collector plates and 2 rubber with gas flow path
Hot device is clamped and around will fixed with bolt successively, and the bolt is tightened to them with predetermined surface pressure (4N), has made solid
Element cell (be also denoted as below " element cell (1) ") (element cell area of body high molecular fuel battery:25cm2)。
(7) I-E characteristic evaluation
Fuel cell evaluation under common humidified condition (following, to be also simply designated as " humidified condition "), is by unit
Battery (1) temperature adjustment is 80 DEG C, is 80 DEG C by anode humidifier temperature adjustment and is 80 DEG C by cathode humidifier temperature adjustment.Then, respectively to
Anode-side supplies the hydrogen as fuel and supplies air to cathode side, have rated the current-voltage (I-V) of element cell (1)
Characteristic.In addition, the fuel cell evaluation under low humidified condition, be by said units battery (1) temperature adjustment be 65 DEG C, anode is added
Wet device temperature adjustment is 65 DEG C and negative electrode temperature adjustment is 65 DEG C of no humidification, have rated current-voltage (I-V) characteristic.
(8) current potential cyclic durability is tested
The experiment of current potential cyclic durability is carried out under the following conditions.
It is being 80 DEG C by element cell (1) temperature adjustment, by anode humidifier temperature adjustment is being 80 DEG C and by cathode humidifier temperature adjustment is
In the state of 80 DEG C, hydrogen supplied to anode-side respectively, supply nitrogen to cathode side, and be applied with 2000 times by 1.0V-
The triangular wave current potential circulation that 1.5V and 1.5V-1.0V is constituted.
In addition, before and after applying 2000 current potential circulations in current potential cyclic durability experiment, having carried out described add
I-E characteristic evaluation under the conditions of wet.As shown in following formula, before and after applying, 0.2A/cm will be circulated by current potential2When
The ratio between the magnitude of voltage that current-voltage measure is obtained (%) is defined as voltage retention.
Voltage retention=(magnitude of voltage after current potential circulation application)/(magnitude of voltage before current potential circulation application) × 100
Here, in the I-V characteristic of fuel cell, magnitude of voltage during a certain constant current density turns into the fuel cell
Power generation performance index.That is, described initial voltage is higher, it is meant that the power generation performance at initial stage of fuel cell is higher, Jin Erbiao
Show that the catalyst activity of oxygen reduction catalyst is higher.In addition, the voltage retention is higher, the generating of fuel cell is represented
The catalyst activity of energy and oxygen reduction catalyst is more difficult to deteriorate, i.e., durability is higher.By 0.2A/cm2When humidified condition
Table 1 is shown in the initial voltage and voltage retention under low humidified condition.
[embodiment 2]
Carbon particle B (1) is obtained similarly to Example 1, and carbon material (1) and carbon particle B (1) have been mixed to get catalysis
Agent carrier (2).Wherein, relative to the gross mass of catalyst carrier (2), the ratio shared by the carbon particle B (1) is set to 70 matter
Measure %.In addition, the mol ratio of the element in catalyst carrier (2), when titanium is set into 1, carbon is that 11.15, nitrogen is that 0.04, oxygen is
1.96。
After, platinum and cobalt are supported to catalyst carrier (2) similarly to Example 1, carrying out heat treatment makes platinum and cobalt alloy
Change, obtain electrode catalyst (2), and carried out the making and its evaluation of fuel cell.Show the result in table 1.
[embodiment 3]
Carbon particle B (1) is obtained similarly to Example 1, and carbon material (1) and carbon particle B (1) have been mixed to get catalysis
Agent carrier (3).Wherein, relative to the gross mass of catalyst carrier (3), the ratio shared by the carbon particle B (1) is set to 30 matter
Measure %.In addition, the mol ratio of the element in catalyst carrier (2), when titanium is set into 1, carbon is that 30, nitrogen is that 0.04, oxygen is
1.96。
After, platinum and cobalt are supported to catalyst carrier (3) similarly to Example 1, carrying out heat treatment makes platinum and cobalt alloy
Change, obtain electrode catalyst (3), and carried out the making and its evaluation of fuel cell.Show the result in table 1.
[embodiment 4]
Carbon material (1) is substituted, commercially available carbon material (2) (BET specific surface area 563m is used2/ g, DBP oil absorptions 295mL/
100g, crystallite dimension 3.2nm, carbon nano-particles, which are connected, has the carbon material of chain structure), operate, obtain similarly to Example 1
Catalyst carrier (4) is arrived.Wherein, relative to the gross mass of catalyst carrier (4), the ratio shared by the carbon particle B (1) is set
For 30 mass %.In addition, the mol ratio of the element in catalyst carrier (5), when titanium is set into 1, carbon is that 24.33, nitrogen is
0.04th, oxygen is 1.96.
After, platinum and cobalt are supported to catalyst carrier (4) similarly to Example 1, carrying out heat treatment makes platinum and cobalt alloy
Change, obtain electrode catalyst (4), and carried out the making and its evaluation of fuel cell.Show the result in table 1.
[embodiment 5]
In embodiment 1, carbon material (1) is substituted, commercially available carbon material (BET specific surface area 1350m is used2/ g) and carbon materials
Expect (3) (by commercially available carbon black in N2Under atmosphere the Graphon obtained for 4 hours, BET specific surface area are burnt till with 2200 DEG C
170m2/ g, primary particle size 40nm, crystallite dimension 3.5nm, carbon nano-particles have the carbon material of chain structure) mixture (matter
Amount is than being carbon material (1):Carbon material (3)=5:5th, BET specific surface area 760m2/G) (hereinafter, also referred to as " carbon material (4) "), with
Embodiment 1 is similarly operated, and has obtained catalyst carrier (5).Wherein, relative to the gross mass of catalyst carrier (5), the carbon
Ratio shared by particle B (1) is set to 30 mass %.
After, platinum and cobalt are supported to catalyst carrier (5) similarly to Example 1, carrying out heat treatment makes platinum and cobalt alloy
Change, obtain electrode catalyst (5), and carried out the making and its evaluation of fuel cell.Show the result in table 1.
[embodiment 6]
In embodiment 1, carbon material (1) is substituted, commercially available carbon material (BET specific surface area 1350m is used2/ g) and carbon materials
(mass ratio is commercially available carbon material to the mixture of material (3):Carbon material (3)=2:1st, BET specific surface area 955m2/ g) (it is following,
It is designated as " carbon material (5) "), operate similarly to Example 1, obtained catalyst carrier (6).Wherein, carried relative to catalyst
The gross mass of body (6), the ratio shared by the carbon particle B (1) is set to 70 mass %.
After, platinum and cobalt are supported to catalyst carrier (6) similarly to Example 1, carrying out heat treatment makes platinum and cobalt alloy
Change, obtain electrode catalyst (6), and carried out the making and its evaluation of fuel cell.Show the result in table 1.
[embodiment 7]
(carbon particle B (2) making)
In embodiment 1, it is 100 volume %'s to substitute the hydrogen of the hydrogen containing 4 volume % and the mixed gas of nitrogen using nitrogen
Nitrogen, has obtained carbon particle B (2).Carbon particle B (1) is substituted using carbon particle B (2), operates, obtains similarly to Example 1
Catalyst carrier (7).Wherein, relative to the gross mass of catalyst carrier (7), the ratio shared by the carbon particle B (2) is set to 50
Quality %.
After, platinum and cobalt are supported to catalyst carrier (7) similarly to Example 1, carrying out heat treatment makes platinum and cobalt alloy
Change, obtain electrode catalyst (7), and carried out the making and its evaluation of fuel cell.Show the result in table 1.
[comparative example 1]
In embodiment 1, carbon particle B (1) is substituted, using the TiO 2 particles of the raw material for carbon particle B (1), is obtained
Catalyst carrier (8) is arrived.In addition, the gross mass relative to catalyst carrier (8) sets the ratio shared by TiO 2 particles
For 50 mass %.The mol ratio of element in catalyst carrier (8), when titanium is set into 1, carbon is that 20.16, nitrogen is that 0.0, oxygen is
2.0。
After, platinum and cobalt are supported to catalyst carrier (8) similarly to Example 1, carrying out heat treatment makes platinum and cobalt alloy
Change, obtain electrode catalyst (8), and carried out the making and its evaluation of fuel cell.Show the result in table 1.
[comparative example 2]
Alternative catalysts carrier (1) uses carbon material (1) as catalyst carrier (9), carries out and embodiment 1 in addition
Same operation, has obtained electrode catalyst (9).
After, the making and its evaluation of fuel cell have been carried out similarly to Example 1.Show the result in table 1.
[comparative example 3]
Alternative catalysts carrier (1) uses carbon particle B (1) as catalyst carrier (10), carries out in addition with implementing
The same operation of example 1, has obtained electrode catalyst (10).
After, the making and its evaluation of fuel cell have been carried out similarly to Example 1.Show the result in table 1.
[comparative example 4]
In embodiment 1, alternative catalysts carrier (1) uses carbon material (3) as catalyst carrier (11), in addition
Operation similarly to Example 1 is carried out, electrode catalyst (11) has been obtained.
After, the making and its evaluation of fuel cell have been carried out similarly to Example 1.Show the result in table 1.
[comparative example 5]
(carbon particle B (3) making)
In embodiment 1, replacement of titanium dioxide particle using commercially available di-iron trioxide particle (average grain diameter 10~
15nm), the operation same with embodiment is carried out, the oxide carbon for having obtained the internal package di-iron trioxide particle of carbon is answered
Conjunction particle (hereinafter, also referred to as " carbon particle B (3) ").
Carbon particle B (1) is substituted using carbon particle B (3), operates similarly to Example 1, has obtained catalyst carrier
(12).Wherein, relative to the gross mass of catalyst carrier (12), the ratio shared by the carbon particle B (3) is set to 50 mass %.
After, platinum and cobalt are supported to catalyst carrier (12) similarly to Example 1, carrying out heat treatment makes platinum and cobalt alloy
Change, obtain electrode catalyst (12), and carried out the making and its evaluation of fuel cell.Show the result in table 1.
Table 1-3
As shown in table 1, in embodiment 1~7, compared with comparative example, it is changed into low from the operation under common humidified condition and adds
Hydraulic performance decline during operation under the conditions of wet is small, in addition, voltage retention is also high, can obtain high-durability.
Moreover, embodiment 1~3 and embodiment 5~7 show high living under common humidified condition and under low humidified condition
Property.It is thought that because selection has used BET specific surface area, DBP oil absorptions and crystallite dimension to be respectively adapted to carbon of the invention
Material.In addition, embodiment 5 and embodiment 6 show particularly be changed into low humidified condition from the operation under common humidified condition
Under operation when hydraulic performance decline it is small, show high-durability.It is thought that being used in mixed way BET due to properly selecting and comparing surface
Product, the primary particle size 2 kind carbon materials different with crystallite dimension.
<Industrial applicability>
The electrode catalyst of present invention hydraulic performance decline under low humidified condition is small and shows high-durability, therefore available
Generating efficiency and fuel cell of excellent in reliability.The fuel cell can be used as electronic power supply on vehicle, home-use cogeneration
The power utilization of system etc..
Claims (24)
1. a kind of catalyst carrier, includes the carbon material for the chain structure being connected with carbon particle,
The catalyst carrier includes titanium compound carbon compound particle, and the titanium compound carbon compound particle is the internal package in carbon
Obtained from the particle of titanium compound,
The mol ratio of element in catalyst carrier, when titanium is set into 1, carbon be more than 0 and be less than 50, nitrogen be more than 0 and be 2 with
Under, oxygen be more than 0 and for less than 3.
2. catalyst carrier according to claim 1, dibutyl phthalate oil absorption is 150~450mL/100g.
3. catalyst carrier according to claim 1 or 2, the content of the particle of the titanium compound is 10~90 matter
Measure %.
4. the catalyst carrier according to any one of claims 1 to 3, BET specific surface area is 450~1100m2/g。
5. the catalyst carrier according to any one of Claims 1 to 4, the average grain diameter of the particle of the titanium compound is
5~300nm.
6. the catalyst carrier according to any one of Claims 1 to 5, interior in the titanium compound carbon compound particle
The carbon of the particle of portion's parcel titanium compound is at least one kind of carbon in amorphous carbon and graphitized carbon.
7. the catalyst carrier according to any one of claim 1~6, the carbon material is selected from carbon black, graphitized charcoal
Wantonly a kind in black, graphite and porous carbon.
8. the catalyst carrier according to any one of claim 1~6, the carbon material is to be selected from carbon black, graphitized charcoal
Two or more any mixture for mixing in black, graphite and porous carbon.
9. the catalyst carrier according to any one of claim 1~8, the primary particle size of the carbon material for 5~
300nm。
10. a kind of electrode catalyst, is to the catalyst-loaded metal of catalyst carrier described in any one of claim 1~9
Obtained from particle.
11. electrode catalyst according to claim 10, the metals of the catalyst metal particles be selected from platinum, palladium, ruthenium,
At least one kind of metal in gold, rhodium, iridium, osmium, iron, cobalt, nickel, chromium, zinc and tantalum or by least two kinds of metals in these metals
The alloy of composition.
12. the electrode catalyst according to claim 10 or 11, BET specific surface area is 200~800m2/g。
13. a kind of electrode, has:Electrode matrix and the catalyst layer formed on the electrode matrix, the catalyst layer are included
The electrode catalyst that any one of claim 10~12 is recorded.
14. a kind of membrane-electrode assembly, is that negative electrode and anode are configured across dielectric film,
At least one party of the negative electrode and the anode is the electrode described in claim 13.
15. a kind of fuel cell, possesses the membrane-electrode assembly described in claim 14.
16. a kind of manufacture method of catalyst carrier, is the catalyst carrier described in any one of manufacturing claims 1~9
Method, including:
By the particle of the carbon material for the chain structure being connected with carbon particle and the internal package titanium compound of carbon
The process of titanium compound carbon compound particle mixing,
The ratio between element in the titanium compound carbon compound particle, when titanium is set into 1, carbon is more than 0 and is more than 0 for less than 7, nitrogen
And be that less than 2, oxygen is more than 0 and be less than 3.
17. the manufacture method of catalyst carrier according to claim 16, relative to the titanium compound carbon of 1 mass parts
Compound particle, mixes the carbon material of 0.1~10 mass parts.
18. the manufacture method of the catalyst carrier according to claim 16 or 17, the BET specific surface area of the carbon material is
700~1400m2/g。
19. the manufacture method of the catalyst carrier according to any one of claim 16~18, the adjacent benzene of the carbon material
Dibutyl carboxylic acid oil absorption is 350~550mL/100g.
20. the manufacture method of the catalyst carrier according to any one of claim 16~19, the crystallite of the carbon material
Size is 0.6~2.0nm.
21. the manufacture method of the catalyst carrier according to claim 16 or 17, the carbon material is that BET specific surface area is
700~1400m2/ g carbon material X and BET specific surface area is 100~500m2/ g carbon material Y mixture.
22. the manufacture method of catalyst carrier according to claim 21, the primary particle size of the carbon material Y for 5~
300nm, and crystallite dimension is 2.0~5.0nm.
23. the manufacture method of the catalyst carrier according to any one of claim 16~22, by the way that titanium carbon nitrogen will be selected from
At least one kind of compound in oxide, titanyl nitride and titanium oxide is mixed with polyvinylpyrrolidone, in non-oxidizing gas
It is heat-treated under atmosphere with 500~1100 DEG C, obtains the titanium compound carbon compound particle.
24. the manufacture method of the catalyst carrier according to any one of claim 16~23, the grain of the titanium compound
The BET specific surface area of son is 50~300m2/g。
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JP6819982B2 (en) | 2016-02-26 | 2021-01-27 | 日清紡ホールディングス株式会社 | Carbon catalyst for redox flow battery electrodes |
US11114684B2 (en) * | 2016-04-28 | 2021-09-07 | Kolon Industries, Inc. | Fuel cell membrane-electrode assembly |
JP6727265B2 (en) * | 2018-09-18 | 2020-07-22 | 株式会社キャタラー | Anode catalyst layer for fuel cell and fuel cell using the same |
US20210399312A1 (en) * | 2018-11-01 | 2021-12-23 | The Regents Of The University Of California | High stability platinum-based electrochemical catalysts |
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EP1164651A1 (en) | 2000-06-12 | 2001-12-19 | Asahi Glass Co., Ltd. | Electrode catalyst for polymer electrolyte fuel cell and method for its production |
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JP5106342B2 (en) * | 2008-10-06 | 2012-12-26 | 昭和電工株式会社 | Catalyst, method for producing the same and use thereof |
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